JPH0639285A - Photocatalyst - Google Patents
PhotocatalystInfo
- Publication number
- JPH0639285A JPH0639285A JP4196910A JP19691092A JPH0639285A JP H0639285 A JPH0639285 A JP H0639285A JP 4196910 A JP4196910 A JP 4196910A JP 19691092 A JP19691092 A JP 19691092A JP H0639285 A JPH0639285 A JP H0639285A
- Authority
- JP
- Japan
- Prior art keywords
- fe2o3
- photocatalyst
- tio2
- bulk
- photocatalytic function
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010931 gold Substances 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910001922 gold oxide Inorganic materials 0.000 claims description 3
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 3
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000010970 precious metal Substances 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 230000005476 size effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract description 2
- 229910052737 gold Inorganic materials 0.000 abstract 2
- 239000011882 ultra-fine particle Substances 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- -1 argon ions Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は光触媒に関し、光のエネ
ルギを利用して水を分解する光触媒やＣＯ2固定光触媒
に適用できる光触媒に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalyst, and more particularly to a photocatalyst which decomposes water by utilizing light energy and a photocatalyst applicable to a CO 2 fixed photocatalyst.
【０００２】[0002]
【従来の技術】従来の光触媒にはＴｉＯ2 やＳｒＴｉＯ
3 などがあるが、バンドギャップが３．０eV以上であ
り、利用できる光の波長が４００nm以下であるため太陽
光を利用して水分解を行なう場合、その光の利用効率は
５％程度と低く実用化されていない。このため太陽光の
利用効率が高い光触媒の開発が求められている。 2. Description of the Related Art Conventional photocatalysts include TiO 2 and SrTiO 3.
Although there are 3 etc., the bandgap is 3.0 eV or more, and the wavelength of light that can be used is 400 nm or less, so when using water to decompose water, the light utilization efficiency is low at around 5%. It has not been put to practical use. Therefore, development of a photocatalyst with high utilization efficiency of sunlight is required.
【０００３】酸化鉄（Ｆｅ2 Ｏ3 ）バルクはバンドギャ
ップが２．２eVのため太陽光の利用効率は約１７％と高
い値をもっている。しかし、Ｆｅ2 Ｏ3 は水を分解でき
る電位を有していないため、バルブのままでは光触媒と
しての機能を果たすことができない。Since the band gap of iron oxide (Fe 2 O 3 ) bulk is 2.2 eV, the utilization efficiency of sunlight has a high value of about 17%. However, since Fe 2 O 3 does not have a potential for decomposing water, it cannot function as a photocatalyst if it remains as a bulb.
【０００４】[0004]
【発明が解決しようとする課題】本発明は上記技術水準
に鑑み、一般にバルクでは光触媒機能を有さない物質で
ある酸化鉄（Ｆｅ2 Ｏ3 ）に光触媒機能をもたせ、しか
も従来の光触媒のＴｉＯ 2 よりも太陽光の利用効率が高
く実用的な光触媒を提供しようとするものである。DISCLOSURE OF THE INVENTION The present invention has the above technical level.
In view of this, in general, it is a substance that does not have a photocatalytic function in the bulk.
Some iron oxide (Fe2O3) Has a photocatalytic function,
Also conventional TiO of photocatalyst 2Use of sunlight is higher than
The present invention aims to provide a practical photocatalyst.
【０００５】[0005]
【課題を解決するための手段】本発明は貴金属である
金、白金、パラジウムあるいは二酸化チタンの表面上に
粒径が１０〜１００Åの酸化鉄（Ｆｅ2 Ｏ3 ）を担持固
定させてなることを特徴とする光触媒である。According to the present invention, iron oxide (Fe 2 O 3 ) having a particle size of 10 to 100Å is supported and fixed on the surface of a noble metal such as gold, platinum, palladium or titanium dioxide. It is a featured photocatalyst.
【０００６】[0006]
【作用】半導体が光触媒機能を有するための条件は、
（１）伝導帯の位置がバンドモデルで表わすとき水素発
生電位より上方にあることと、（２）価電子帯の上端が
酸素発生電位よりも下方にあることが必要である。バル
ク酸化鉄（Ｆｅ2 Ｏ3 ）の場合、図２に示すように
（２）の条件は満たしているが、（１）の条件は満たし
ていないため光触媒としての機能を有さない。[Function] The conditions for a semiconductor to have a photocatalytic function are:
It is necessary that (1) the position of the conduction band is above the hydrogen generation potential when expressed by a band model, and (2) that the upper end of the valence band is below the oxygen generation potential. In the case of bulk iron oxide (Fe 2 O 3 ), the condition (2) is satisfied as shown in FIG. 2, but the condition (1) is not satisfied, so that it does not function as a photocatalyst.
【０００７】しかし、本発明においては図３に示すよう
に、酸化鉄（Ｆｅ2 Ｏ3 ）を粒径１０〜１００Å（図３
には粒径３０Åを代表例として示す）に超微粒子化する
ことにより伝導帯の位置は上方へ働き、バルクでは越え
ていなかった水素発生電位の上方に位置することを見い
だした。（粒径１０〜１００Åの粒子は原子数にして数
百、数千になる。これにより粒子の電子状態は通常の原
子数が無限大のバルクとは違ったものとなる。一般に、
この現象を量子サイズ効果と呼んでいる。）これによっ
て、（１）の条件を満たすようになる。また価電子帯も
量子効果によって変化するがバルクのときの価電子帯の
位置が酸素発生電位よりかなり下方に位置したため、
（２）の条件を破ることはないことを見いだし本発明に
至ったものである。However, in the present invention, as shown in FIG. 3, iron oxide (Fe 2 O 3 ) has a particle size of 10 to 100Å (see FIG. 3).
The particle size of 30 Å is shown as a typical example), and it was found that the position of the conduction band works upward and that it is located above the hydrogen generation potential which was not exceeded in the bulk. (A particle with a particle size of 10 to 100Å has hundreds or thousands of atoms. Due to this, the electronic state of the particle is different from the usual bulk with an infinite number of atoms.
This phenomenon is called the quantum size effect. By this, the condition of (1) is satisfied. The valence band also changes due to the quantum effect, but since the position of the valence band in the bulk was located well below the oxygen generation potential,
The inventors have found that the condition of (2) is not violated and have reached the present invention.
【０００８】さらに太陽光の利用効率について述べる。
図４に示すように、一般に超微粒子化によって価電子
帯、伝導帯の幅であるバンドギャップは増大する。Ｆｅ
2 Ｏ3の場合、バルクのバンドギャップは約２．２eVで
ある。これを超微粒子化するとバンドギャップは増大し
２．３〜２．４eV程度になる。その結果、図５に示すよ
うに、太陽光の利用効率は約１５％となり、バルクの場
合の約１７％の利用効率と比較すると低くはなるが、実
用に十分耐え得る効率の光触媒となる。Further, the utilization efficiency of sunlight will be described.
As shown in FIG. 4, the band gap, which is the width of the valence band and the conduction band, generally increases due to the formation of ultrafine particles. Fe
For 2 O 3 , the bulk bandgap is about 2.2 eV. If this is made into ultrafine particles, the band gap increases and becomes about 2.3 to 2.4 eV. As a result, as shown in FIG. 5, the utilization efficiency of sunlight is about 15%, which is lower than the utilization efficiency of about 17% in the case of bulk, but it is a photocatalyst having sufficient efficiency for practical use.
【０００９】本発明の光触媒の担体としては酸化、還元
反応に安定な素材であるという理由より金、白金、パラ
ジウム及び二酸化チタンを選択したものである。超微粒
子のＦｅ2 Ｏ3 が触媒反応を起こすためには、これら担
体の表面をできるだけ覆う方がよいが、粒子どうしが接
触すると量子サイズ効果が起こらなくなるため、超微粒
子Ｆｅ2 Ｏ3 の担体表面占有率は最大５０％程度にする
べきであり、一般的には１０〜５０％の占有率であるこ
とが好ましい。As the carrier for the photocatalyst of the present invention, gold, platinum, palladium and titanium dioxide are selected because they are stable materials against oxidation and reduction reactions. In order for ultrafine particles of Fe 2 O 3 to cause a catalytic reaction, it is preferable to cover the surface of these carriers as much as possible, but when the particles contact each other, the quantum size effect does not occur, so the surface of the ultrafine particles of Fe 2 O 3 is not supported. The occupancy rate should be about 50% at maximum, and generally, the occupancy rate is preferably 10 to 50%.
【００１０】[0010]
【実施例】本発明の光触媒の一実施例の製造方法につい
て説明する。先ず、３０Åの酸化鉄（Ｆｅ2 Ｏ3 ）をＴ
ｉＯ2 電極上に分散生成させる。その方法はＦｅ2 Ｏ3
ターゲットをイオン銃を用いたアルゴンイオンにてスパ
ッタし、ＴｉＯ2 電極上に生成させる。粒径制御は水晶
振動子式の成膜モニタにて監視して行なった。スパッタ
条件は下記の通りである。イオンビームは加速電圧１k
V、イオン電流１０mA、ターゲット面に対して４５°で
入射した。ＴｉＯ2 基板電極はターゲット面の垂直上方
に置き、基板温度は室温に保った。なお、このときの作
動真空度は２×１０-4Torrであった。作成した試料を図
１，２に示す。図１は外観模式図、図２は図１の断面図
である。EXAMPLE A method for producing an embodiment of the photocatalyst of the present invention will be described. First, 30Å iron oxide (Fe 2 O 3 ) was added to T
Disperse and generate on the iO 2 electrode. The method is Fe 2 O 3
The target is sputtered with argon ions using an ion gun to generate it on the TiO 2 electrode. The grain size was controlled by monitoring with a crystal oscillator type film formation monitor. The sputtering conditions are as follows. Ion beam acceleration voltage is 1k
V, ion current 10 mA, incident at 45 ° to target surface. The TiO 2 substrate electrode was placed vertically above the target surface and the substrate temperature was kept at room temperature. The working vacuum at this time was 2 × 10 −4 Torr. The prepared sample is shown in FIGS. 1 is a schematic external view, and FIG. 2 is a sectional view of FIG.
【００１１】また真空蒸着法においては、真空度１×１
０-6のもとで行ない抵抗加熱法にてＦｅを蒸発させ上部
基板上に水晶振動子成膜モニタの監視のもとで粒径制御
を行ないつつ作成した。これを大気中５００℃で加熱処
理することで、作成を行なった。作成された試料は前記
図１，図２と同様なものである。In the vacuum deposition method, the degree of vacuum is 1 × 1.
Fe was evaporated by a resistance heating method under 0 -6 , and the grain size was controlled on the upper substrate while controlling the grain size under the monitor of the crystal oscillator film deposition monitor. It was created by heating this at 500 ° C. in the atmosphere. The prepared sample is similar to that shown in FIGS.
【００１２】作成した試料は以下の電気化学計測により
評価した。電気化学測定用電解セルは作用電極として上
記試料を用い、対極には白金を、また参照電極には銀・
塩化銀電極を使用した。溶液は１規定水酸化ナトリウム
水溶液をもちいた。このセルを使用し、ロックインアン
プ内蔵の周波数応答器とポテンショスタットを組み合わ
せた装置にて、複素インピーダンスを計測し、この複素
インピーダンスプロットのデータを用い、Mott-Schottk
y プロットよりフラットバンドポテンシャルを求めた。
またバンドギャップは分光光度計の透過率測定より導出
した。The prepared sample was evaluated by the following electrochemical measurement. The electrochemical measurement electrolytic cell uses the above sample as a working electrode, platinum as the counter electrode, and silver as the reference electrode.
A silver chloride electrode was used. The solution used was a 1N aqueous sodium hydroxide solution. Using this cell, the complex impedance was measured by the device that combined the frequency response device with built-in lock-in amplifier and the potentiostat, and the data of this complex impedance plot was used to calculate the Mott-Schottk
The flat band potential was obtained from the y plot.
The band gap was derived from the transmittance measurement of a spectrophotometer.
【００１３】前記図３に示したように、Ｆｅ2 Ｏ3 バル
クの伝導帯のエネルギ準位は＋０．２（V vs NHE）であ
ったものが粒径３０Åの超微粒子の場合、−０．２（V
vs NHE) になり、水素発生電位よりも、上方に位置する
ようになった。また、価電子帯の位置はバルクの時は、
＋２．４（V vs NHE）にあったものが、超微粒子化する
ことによって、＋２．１（V vs NHE）に変化した。この
状態は粒径３０ÅのＦｅ2 Ｏ3 超微粒子が光触媒として
の条件を満たしていることを示す。As shown in FIG. 3, when the energy level of the conduction band of the Fe 2 O 3 bulk is +0.2 (V vs NHE), it is −0. 2 (V
vs NHE), and it is located above the hydrogen evolution potential. Also, the position of the valence band is in the bulk,
What was at +2.4 (V vs NHE) changed to +2.1 (V vs NHE) due to ultrafine particles. This state indicates that the Fe 2 O 3 ultrafine particles having a particle size of 30 Å satisfy the conditions as a photocatalyst.
【００１４】また、前記図４に示したように、バンドギ
ャップはバルクで２．２eVであったものが、粒径３０Å
の超微粒子では、２．３eVになり、このときの太陽光利
用効率は前記図５に示したように約１５％になった。Further, as shown in FIG. 4, the band gap was 2.2 eV in bulk, but the particle size was 30 Å
In the case of the ultrafine particles, the solar light utilization efficiency was 2.3 eV, and the solar light utilization efficiency at this time was about 15% as shown in FIG.
【００１５】[0015]
【発明の効果】本発明により、バルクでは光触媒として
の能力をもたない酸化鉄Ｆｅ2 Ｏ3 を光触媒として使用
しうるようになり、その工業的効果は顕著なものがあ
る。INDUSTRIAL APPLICABILITY According to the present invention, iron oxide Fe 2 O 3 which has no ability as a photocatalyst in bulk can be used as a photocatalyst, and its industrial effect is remarkable.
【図１】本発明の一実施例の光触媒の外観模式図。FIG. 1 is a schematic external view of a photocatalyst according to an embodiment of the present invention.
【図２】図１の断面図。FIG. 2 is a sectional view of FIG.
【図３】Ｆｅ2 Ｏ3 バルクと粒径３０Å超微粒子Ｆｅ2
Ｏ3 の伝導体および価電子帯の位置を示す図。Fig. 3 Fe 2 O 3 bulk and particle size 30 Å ultrafine Fe 2
Shows the position of the conductor and the valence band of O 3.
【図４】Ｆｅ2 Ｏ3 粒子の粒径変化によるバンドギャッ
プの変化を示す図。FIG. 4 is a diagram showing a change in band gap due to a change in particle size of Fe 2 O 3 particles.
【図５】Ｆｅ2 Ｏ3 超微粒子光触媒の太陽エネルギ変換
効率をＦｅ2 Ｏ3 バルクおよび従来のＴｉＯ2 光触媒と
対比して示す図。FIG. 5 is a graph showing the solar energy conversion efficiency of Fe 2 O 3 ultrafine particle photocatalysts in comparison with Fe 2 O 3 bulk and conventional TiO 2 photocatalysts.
Claims (1)
いは二酸化チタンの表面上に粒径が１０〜１００Åの酸
化鉄（Ｆｅ2 Ｏ3 ）を担持固定させてなることを特徴と
する光触媒。1. A photocatalyst comprising a precious metal, such as gold, platinum, palladium or titanium dioxide, on which iron oxide (Fe 2 O 3 ) having a particle diameter of 10 to 100 Å is supported and fixed on the surface thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4196910A JPH0639285A (en) | 1992-07-23 | 1992-07-23 | Photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4196910A JPH0639285A (en) | 1992-07-23 | 1992-07-23 | Photocatalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0639285A true JPH0639285A (en) | 1994-02-15 |
Family
ID=16365693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4196910A Withdrawn JPH0639285A (en) | 1992-07-23 | 1992-07-23 | Photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0639285A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996013327A1 (en) | 1994-10-31 | 1996-05-09 | Kanagawa Academy Of Science And Technology | Titanium oxide photocatalyst structure and method of manufacturing the same |
| WO1997026991A1 (en) * | 1996-01-22 | 1997-07-31 | Petroleum Energy Center | Photocatalyst, method of producing the photocatalyst, and photocatalytic reaction method |
| US5759948A (en) * | 1994-02-07 | 1998-06-02 | Ishihara Sangyo Kaisha Ltd. | Titanium oxide for photocatalyst and method of producing the same |
| US5865088A (en) * | 1995-07-25 | 1999-02-02 | Komatsu Ltd. | High-speed safety circuit for a hydraulic press |
| US6003429A (en) * | 1995-07-06 | 1999-12-21 | Komatsu Ltd. | High speed and high-load cylinder device and method for controlling the same |
| EP1036593A1 (en) * | 1999-03-16 | 2000-09-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Titanium dioxide photocatalyst with Fe3+ ions added thereon |
| US6939611B2 (en) | 1994-10-31 | 2005-09-06 | Kanagawa Academy Of Science And Technology | Window glass employing titanium dioxide photocatalyst |
| CN105618037A (en) * | 2015-12-25 | 2016-06-01 | 西北大学 | Titanium dioxide-silver composite photocatalysis film and preparing method and application thereof |
| CN106881155A (en) * | 2016-12-29 | 2017-06-23 | 广州凯耀资产管理有限公司 | A kind of Au/TiO2/ metal organic framework composite photo-catalyst and preparation method and application |
| JP2019172499A (en) * | 2018-03-28 | 2019-10-10 | 富士フイルム株式会社 | Gel and hydrogen-generating pack |
-
1992
- 1992-07-23 JP JP4196910A patent/JPH0639285A/en not_active Withdrawn
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5759948A (en) * | 1994-02-07 | 1998-06-02 | Ishihara Sangyo Kaisha Ltd. | Titanium oxide for photocatalyst and method of producing the same |
| US7157840B2 (en) | 1994-10-31 | 2007-01-02 | Kanagawa Academy Of Science And Technology | Illuminating devices employing titanium dioxide photocatalysts |
| US6939611B2 (en) | 1994-10-31 | 2005-09-06 | Kanagawa Academy Of Science And Technology | Window glass employing titanium dioxide photocatalyst |
| WO1996013327A1 (en) | 1994-10-31 | 1996-05-09 | Kanagawa Academy Of Science And Technology | Titanium oxide photocatalyst structure and method of manufacturing the same |
| US7327074B2 (en) | 1994-10-31 | 2008-02-05 | Kanagawa Academy Of Science And Technology | Illuminating devices employing titanium dioxide photocatalysts |
| US6003429A (en) * | 1995-07-06 | 1999-12-21 | Komatsu Ltd. | High speed and high-load cylinder device and method for controlling the same |
| US5865088A (en) * | 1995-07-25 | 1999-02-02 | Komatsu Ltd. | High-speed safety circuit for a hydraulic press |
| JPH09262482A (en) * | 1996-01-22 | 1997-10-07 | Sekiyu Sangyo Kasseika Center | Photocatalyst, method for producing photocatalyst, and method for photocatalytic reaction |
| WO1997026991A1 (en) * | 1996-01-22 | 1997-07-31 | Petroleum Energy Center | Photocatalyst, method of producing the photocatalyst, and photocatalytic reaction method |
| US6077492A (en) * | 1996-01-22 | 2000-06-20 | Petroleum Energy Center | Photocatalyst, process for producing the photocatalyst, and photocatalytic reaction method |
| EP1036593A1 (en) * | 1999-03-16 | 2000-09-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Titanium dioxide photocatalyst with Fe3+ ions added thereon |
| CN105618037A (en) * | 2015-12-25 | 2016-06-01 | 西北大学 | Titanium dioxide-silver composite photocatalysis film and preparing method and application thereof |
| CN106881155A (en) * | 2016-12-29 | 2017-06-23 | 广州凯耀资产管理有限公司 | A kind of Au/TiO2/ metal organic framework composite photo-catalyst and preparation method and application |
| JP2019172499A (en) * | 2018-03-28 | 2019-10-10 | 富士フイルム株式会社 | Gel and hydrogen-generating pack |
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